Organoboranes for synthesis. 9. Rapid reaction of organoboranes with iodine under the influence of base. a convenient procedure for the conversion of alkenes into iodides via hydroboration |
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| Institution: | 1. Centre Interdisciplinaire de Nanoscience de Marseille, Aix Marseille Université, CNRS, CINaM UMR 7325, case 913, 163 Ave de Luminy, 13288 Marseille cedex 09, France;2. Laboratoire Matériaux Polymères-Interfaces-Environnement Marin-MAPIEM—EA 4323, Université de Toulon, 83957 La Garde, France;1. Department of Life Sciences, National University of Kaohsiung, Kaohsiung 811, Taiwan;2. Department of Microbiology, Kaohsiung Medical University, Kaohsiung 807, Taiwan;3. Department of Marine Biotechnology and Resources, National Sun Yat-Sen University, Kaohsiung 804, Taiwan;4. Center of Asia-Pacific Marine Researches, National Sun Yat-sen University, Kaohsiung, Taiwan;1. Department of Organic Chemistry, Faculty of Pharmacy, Medical University of Warsaw, Banacha 1, 02 097 Warsaw, Poland;2. Department of Crystallography, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60 780 Poznań, Poland;3. Department of Histology and Embryology, First Faculty of Medicine, Medical University of Warsaw, Chałubiński 5, 02 004 Warsaw, Poland;1. Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China;2. Key Laboratory of Drug Targeting and Novel Delivery System of the Ministry of Education, West China School of Pharmacy, Sichuan University, Chengdu 610041, China;1. Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstraße 5–13, Munich, 81377, Germany;2. Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria |
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| Abstract: | The reaction of organoborane with iodine is strongly accelerated by sodium hydroxide. Organoboranes derived from terminal alkenes react with the utilization of approximately two of the three alkyl groups attached to boron, providing a maximum of 67% yield of alkyl iodide. Thus, hydroboration-iodination of 1-decene gives a 60% yield ofn-decyl iodide. Secondary alkyl groups, derived from internal alkenes, react more sluggishly and only one of the three alkyl groups attached to boron is converted to the iodide. Thus, the procedure applied to 2-butene provides a 30% yield of 2-butyl iodide. The use of disiamylboranebis-(3-methyl-2-butylborane, Sia2BH) as hydroborating agent increases the yield of iodides from terminal alkenes since the primary alkyl groups react in preference to the secondary siamyl groups. Consequently, hydroboration of 1-decene with Sia2BH, followed by iodination gives a 95% yield ofn-decyl iodide. The use of methanolic sodium methoxide in place of sodium hydroxide provides alkyl iodides in considerably higher yields. The combination of hydroboration with iodination in the presence of a base provides a convenient method for theanti-Markovnikov hydroiodination of alkenes. The base-induced iodination of organoboranes proceeds with the inversion of configuration at the reaction center, as shown by the formation ofendo-2iodonorbomane from tri-exo-norbomylborane. |
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